Heat transfer fluid compositions for low temperature applications

ABSTRACT

A heat transfer fluid composition and process employing composite mixtures of terpenes and silicones useful for heat transfer processes in a temperature range down to −200° F., where the fluid heat transfer composition retains its liquid phase over the entire temperature range.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. patent applicationSer. No. 08/674,348, filed Jul. 2, 1996, now U.S. Pat. No. 6,086,782.

FIELD OF THE INVENTION

The invention relates to the field of heat transfer processes.Specifically, the invention concerns low temperature heat transferliquids suitable for use in heat transfer processes for the transfer ofthermal energy at temperatures significantly below 0° F. by means of aspecially formulated low temperature heat transfer fluid composition.More specifically, the invention relates to heat transfer fluidcompositions comprising blends containing a terpene component,comprising at least one terpene, and an alkylbenzene component,comprising at least one alkylbenzene. A later description of other lowtemperature heat transfer fluid compositions containing a terpenecomponent, comprising at least one terpene, and a low viscosity siliconefluid will follow.

BACKGROUND OF THE INVENTION

There are many conventional heat transfer processes which act totransfer thermal energy to or from an object though physical contactwith a heat transfer liquid which is either at a temperature hotter orcolder than the object. A number of organic solvents have been used assuch heat transfer liquids, for example, Dowtherm for high temperatureheat transfer processes and low molecular weight alcohols, ketones andhalogenated hydrocarbons for low temperature heat transfer processes.

Low temperature heat transfer processes continue to have difficultiescaused by the volatility, toxicity, flammability, foaming or lowtemperature viscosity changes of the conventional low temperatureorganic heat transfer liquids. Such conventional low temperature heattransfer liquids exhibit considerable viscosity change or freezing andfoaming as their temperature is reduced. Furthermore, the freezing andboiling points of these heat transfer liquids necessarily restrict theoperational temperature range of the heat transfer processes in whichthey are used.

Heat transfer liquids which might otherwise be useful may exhibit toohigh a freezing point or too low a boiling point, or both, to beefficiently employed in low temperature heat transfer processes.Specifically, the freezing or gelation of a low temperature heattransfer liquid will likely lead to a significant reduction in theefficiency of the thermal energy transfer. This reduction in efficiencywill result from significant viscosity increases as well as clogging oftransfer lines or other parts of the heat transfer apparatus which willact to interrupt or impede the circulation of the heat transfer liquidwithin the heat transfer process equipment.

Also, some conventional low temperature heat transfer liquids such asacetone, absorb moisture present in their surroundings. Thus, heattransfer processes employing such fluids may be adversely affected by arise in the freezing point temperature due to the absorption ofmoisture. Accordingly, the absorbed moisture (water) may constitute adisadvantage for low temperature heat transfer processes.

One class of heat transfer liquids known for being beneficial for lowertemperature heat transfer processes (between 0° F. and −142° F.) arecertain chemical compounds of the class of monocyclic terpenes. U.S.Pat. No. 3,597,355 (Hsu) describes the use of monocyclic terpenes as aclass, and d-limonene in particular, as being useful for low temperatureapplications employing heat transfer liquids. The class of monocyclicterpenes is described as consisting of limonene, dipentene, terpinolene,α, β and γ terpinene, among others. The Hsu patent describes d-limoneneas particularly preferred because of its characteristic properties.However, the Hsu patent does not describe the benefits of combining aterpene with an alkylbenzene to produce the composite heat transferfluid compositions of the invention, which exhibit improved lowtemperature operating characteristics.

Monocyclic terpenes are chemical compounds conventionally used assolvents, and also for a variety of other purposes such as the flavoringof foodstuffs. Monocyclic terpenes are described in the Hsu patent asbeing particularly useful in heat transfer processes which employ a heattransfer liquid as a means by which the heat is transferred, but onlywith an example using d-limonene. Such a heat transfer process mightinvolve the circulation, by means of a pump or convection, in a conduitsystem in heat exchange contact with an apparatus from which heat is tobe removed. The heat transfer liquid circulated is maintained at atemperature lower than that of the apparatus to be cooled by a suitablecooling mechanism.

The Hsu patent describes monocyclic terpenes as exhibiting relativelylittle viscosity change over the entire liquid phase temperature range,and thus, can advantageously retain excellent fluidity even at lowtemperatures which are slightly above their respective freezing points.Additionally, monocyclic terpenes have low surface tensions and displayexcellent wetting of metallic and non-metallic surfaces, propertieswhich enhance heat transfer efficiency and minimize ice formation onsuch surfaces.

The specific teaching of the Hsu patent is the use of single monocyclicterpenes for use as heat transfer liquids. Since the grant of the Hsupatent, the cost of orange oil and commercially available limonene (d-or I-) has increased significantly. Furthermore, according to the Hsupatent, naturally occurring limonene is suitable for use as a heatexchange liquid without further refinement. The Hsu patent continues bystating that it is usually desirable to subject naturally occurringlimonene to further distillation to provide relatively pure d-limonenefor use as a heat exchange liquid. Relatively pure d-limonene, however,exhibits a reduction in heat exchange efficiency at temperatures below−120° F. At such temperatures the viscosity of relatively pured-limonene increases significantly. At temperatures below −140° F.,relatively pure d-limonene begins to gel. Such viscosity increase andgelation effectively limits the use of relatively pure d-limonene toheat transfer processes that operate at temperatures above −120° F.

What is needed are heat transfer fluid compositions with improved lowtemperature operating characteristics. Specifically, what is needed areheat transfer fluid compositions which remain in the liquid phase attemperatures from about 0° F. to below −120° F., preferably from about0° F. to about −175° F. for the terpene/alkylbenzene compositions andfrom about 0° F. to about −200° F. for the terpene/siliconecompositions.

SUMMARY OF THE INVENTION

It has been surprisingly found that heat transfer fluid compositionscomprising (a) a terpene component, comprising at least one terpene; and(b) an alkylbenzene component comprising at least one alkylbenzene; aresuitable for use as heat exchange liquids for low temperatureapplications. It has also been unexpectedly determined, with just asmuch surprise, that heat transfer fluid compositions comprising (a) aterpene component, comprising at least one terpene; and (b) a lowviscosity silicone component are also suitable for use as heat exchangefluids for low temperature applications.

It is an object of the invention to provide heat transfer fluidcompositions which exhibit improved performance characteristics underlow temperature conditions, namely compositions which have a wideoperational temperature range in which they remain in the liquid phaseand in which they do not exhibit a significant increase in viscosity orgelation. Such significant viscosity increases and gelation may cause areduction in the efficiency of the heat transfer system in which thefluids are employed by impeding the circulation of the fluid within theheat transfer system apparatus.

It is another object of the invention to provide heat transfer fluidcompositions comprising (a) a terpene component, comprising at least oneterpene; and, (b) an alkylbenzene component, comprising at least onealkylbenzene; wherein the components are provided in an effective amountsuch that the resultant composition remains in the liquid phase attemperatures in the range from about 0° F. to below −120° F., preferablyfrom about 0° F. to about −175° F.

It is another object of the invention to provide heat transfer fluidcompositions wherein the terpene component comprises at least oneterpene selected from the group of terpenes listed in Table 2, andderivatives thereof, and wherein the resultant composition remains inthe liquid phase at temperatures in the range from about 0° F. to below−120° F., preferably from about 0° F. to about −175° F.

It is another object of the invention to provide heat transfer fluidcompositions wherein the terpene component comprises at least oneterpene selected from the group of terpenes consisting of d-limonene,terpinolene, α-terpinene, γ-terpinene, myrcene, 3-carene, sabinene,α-pinene and camphene and wherein the resultant composition remains inthe liquid phase at temperatures in the range from about 0° F. to below−120° F., preferably from about 0° F. to about −175° F.

It is another object of the invention to provide heat transfer fluidcompositions wherein the terpene component comprises at least oneterpene selected from the group of terpenes consisting essentially ofd-limonene and terpinolene and wherein the resultant composition remainsin the liquid phase at temperatures in the range from about 0° F. tobelow −120° F., preferably from about 0° F. to about −175° F.

It is another object of the invention to provide heat transfer fluidcompositions wherein the alkylbenzene component comprises at least onealkylbenzene selected from the group of alkylbenzenes including cumene,diethyl benzene, methyl propyl benzene, propyl benzene and butyl benzeneand wherein the resultant composition remains in the liquid phase attemperatures in the range from about 0° F. to below −120° F., preferablyfrom about 0° F. to about −175° F.

It is still another object of the invention to provide heat transferfluid compositions comprising (a) a terpene component, comprising atleast one terpene; and (b) a low viscosity silicone component whereinthe components are provided in an effective amount such that theresultant composition remains in the liquid phase at temperatures in therange from about 0° F. to below −175° F., preferably from about 0° F. toabout −200° F.

It is another object of the invention to provide a low temperature heattransfer system using a heat transfer liquid comprising (a) transferringthermal energy from the heat transfer liquid to a cooling fluid suchthat the heat transfer liquid is cooled to a temperature between about0° F. and about −175° F.; (b) transferring thermal energy from an objectto be cooled to the heat transfer liquid; and, (c) repeating (a) and (b)until said object is cooled to the desired temperature; wherein the heattransfer liquid consists of a heat transfer fluid composition comprising(a) a terpene component, comprising at least one terpene; and (b) analkylbenzene component, comprising at least one alkylbenzene and whereinsaid components are provided in an effective amount such that theresultant composition remains in the liquid phase at temperatures in therange from about 0° F. to about −175° F. Further, the heat transferliquid may also consist of a heat transfer fluid composition comprising(a) a terpene component, comprising at least one terpene; and (b) a lowviscosity silicone component wherein said components are provided in aneffective amount such that the resultant composition remains in theliquid phase at temperatures in the range from about 0° F. to about−200° F.

BRIEF DESCRIPTION OF THE DRAWINGS

For the purpose of illustrating the invention, forms are shown in thedrawings which are presently preferred. It must be understood, however,that the invention is not limited to the precise arrangements andinstrumentalities shown.

FIG. 1 is a depiction of the experimental apparatus used to test thefreezing and melting point temperature characteristics of the heattransfer fluid compositions of the invention;

FIG. 2 is a chart showing the experimental freezing and meltingtemperature versus time curve for pure (95.6% by weight) d-limonene;

FIG. 3 is a chart showing the experimental freezing/melting temperatureversus time curve for pure (95.6% by weight) d-limonene in comparisonwith the experimental freezing/melting temperature versus time curve fora heat transfer fluid composition consisting of a mixture of d-limoneneand cumene, wherein the composition consists of about 50% by volume ofcumene in d-limonene;

FIG. 4 is a diagrammatic view of a heat transfer process system using aheat transfer fluid composition of the present invention.

FIG. 5. is a chart showing the experimental freezing/melting temperatureversus time curve for pure d-limonene in comparison with theexperimental freezing/melting temperature versus time curve for a heattransfer fluid composition consisting of a mixture of d-limonene andsilicone, wherein the composition consists of about 50% by volume ofsilicone and d-limonene.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The novel heat transfer fluid compositions of the invention exhibit lowfreezing point temperatures and a broad range of temperatures over whichthey retain the liquid phase. Both of these characteristics are verydesirable for low temperature heat transfer fluids. Specifically, theheat transfer fluid compositions of the invention can be used in heattransfer process systems with operating temperatures on the heattransfer liquid side of between about 0° F. and about −120° F.,preferably between about 0° F. and about −175° F., or to about −200° F.,depending upon the fluid composition. Furthermore, the heat transferfluid compositions of the invention allow for a wide range of operatingconditions under which they will not vaporize or freeze.

The following detailed description represents the best presentlycontemplated mode of carrying out the invention. The description is notintended in a limiting sense, and it is made solely for the purpose ofillustrating the general principles of the invention. The variousfeatures and advantages of the present invention may be more readilyunderstood with reference to the following detailed description taken inconjunction with the accompanying drawings and claims.

The term “terpenes” traditionally applied to cyclic hydrocarbons havingstructures with empirical formula C₁₀H₁₆ which occur in the essentialoils of plants. Knowledge of the chemistry of the terpene field hasdeveloped and compounds related both chemically and biogenetically tothe C₁₀H₁₆ carbons have been identified. Some natural products have beensynthesized and other synthetic compounds resemble known terpenestructures. Consequently, the term “terpenes” may now be understood toinclude not only the numerous C₁₀H₁₆ hydrocarbons, but also theirhydrogenated derivatives and other hydrocarbons possessing similarfundamental chemical structures. These hydrocarbons may be acyclic orcyclic, simple or complex, and of natural or synthetic origin. Thecyclic terpene hydrocarbons may be classified as monocyclic, bicyclic,or tricyclic. Many of their carbon skeletons have been shown to consistof multiples of the isoprene nucleus, C₅H₈.

It is known that certain monocyclic terpenes, particularly d-limonene,may be used as heat transfer fluids. Note that in this disclosure theterm d-limonene will be understood to refer to commercially available“d-limonene”. Those skilled in the art will know that commerciallyavailable d-limonene is not 100% pure d-limonene. For example,d-limonene, commercially available as food grade d-limonene from FloridaChemical, was subjected to gas chromatograph analysis which resulted inthe determination of the minor constituent components of the relativelypure d-limonene mixture as shown in Table 1.

TABLE 1 Component % by weight in Chemical Compound Commercial d-limonened-limonene 95.6% octanal 0.4% sabinene 0.7% α-pinene 0.6% myrcene 2.7%

The various compounds recited in Table 1 may be classified as follows:d-limonene is a monocyclic terpene; 3-carene, sabinene and (α-pinene arebicyclic terpenes; myrcene is an acyclic terpene; and octanal is anon-terpene compound.

Experiments were performed on a sample of food grade d-limonene obtainedfrom Florida Chemical. The purpose of these experiments was to determinethe freezing point temperature and melting point temperature of thed-limonene. These tests were performed using the apparatus depicted inFIG. 1. The test apparatus shown in FIG. 1 is called a cryostat. Most ofthe components of the apparatus were fabricated by Loikits IndustrialServices. The principal components of the apparatus are a cold finger ornitrogen evaporator coil (4) made of copper to which liquid nitrogenenters through the liquid nitrogen line (1) and exits through line (2).The cold finger (4) is submerged in a bath of liquid (6) whosefreezing/melting characteristics are to be determined. Agitation ofliquid (6) is provided by a mechanical stirrer (3) connected to a motor(5). Thermocouples (9) are located at different points to measure thetemperatures of the liquid (6) as well as the cold finger (4). The glassdewar (10) is vacuum jacketed to provide insulation from the ambientsurroundings.

The procedure used to determine the freezing/melting pointcharacteristics of the food grade d-limonene follows:

-   1. measuring out about 600 ml of d-limonene;-   2. optionally drying the d-limonene by passing it through a dririte    column;-   3. pouring the 600 ml of d-limonene into a clean dewar (10);-   4. agitating the d-limonene with stirrer (3) rotating at a rate of    about 2,400 rpm;-   5. cooling the d-limonene by initiating the flow of liquid nitrogen    to the cold finger (4) by opening control valve (7);-   6. operating control valve (7) to regulate the flow of liquid    nitrogen to the cold finger (4) such that the temperature difference    between the d-limonene in the dewar and the cold finger does not    exceed 30° F.;-   7. continuing cooling until the d-limonene freezes, or until the    temperature minimum for the apparatus is reached (i.e., continued    cooling does not result in a reduction in the d-limonene    temperature; this minimum temperature has been observed to be about    −175° F. for the test apparatus used);-   8. observing the temperature of the d-limonene when freezing occurs,    if freezing occurs during the cooling phase;-   9. stopping the flow of liquid nitrogen to the cold finger (4) to    allow the d-limonene to warn through absorption of heat from the    ambient surroundings;-   10. observing the temperature of the d-limonene when freezing    occurs, if freezing occurs during the warming phase; and,-   11. optionally heating the d-limonene with heater (8) to speed    melting during the experiment.    The following observations were made during the experiments    performed on the d-limonene. The d-limonene formed a gel phase at    temperatures below about −120° F. It was observed that sudden    gelation occurred at or just below about −130° F. Upon repeating the    experiment, the gelation point was confirmed to be approximately    −130° F. Gelation of commercial d-limonene at the temperature noted    would tend to cause a significant increase in the viscosity of the    d-limonene at such temperatures. Using a temperature driving force    of about 5° F. (i.e., maintaining the temperature of the cooling    element at a temperature about 5° F. colder than the d-limonene) and    providing gentle agitation, it was possible to supercool the    d-limonene to a temperature below −160° F. without freezing. After    cooling the d-limonene in the test apparatus to about −160° F., the    flow of liquid nitrogen to the evaporation coil (4) was stopped and    the d-limonene was allowed to absorb heat from the surrounding    environment at ambient temperature, 65° F. Upon warming the    d-limonene underwent rapid freezing.

The results of the experiments performed on the d-limonene are providedin graphical form in FIG. 2. These experiments demonstrate that thed-limonene tested had a freezing point temperature of about −153° F. anda melting point temperature of about −110° F.

Referring to FIG. 2, this chart graphically demonstrates the temperaturereduction in degrees Fahrenheit against time for d-limonene. The initialliquid phase of the d-limonene tested is shown as Zone I in FIG. 2. Inthe initial liquid phase, the temperature of the d-limonene in theexperimental bath was reduced with data being plotted in FIG. 2beginning at a temperature of approximately −100° F. After approximately19 minutes, the d-limonene was cooled to about −163° F., Point A. Theflow of liquid nitrogen was then stopped and the d-limonene was allowedto warm by absorbing heat from the ambient surroundings. After about 4minutes, the d-limonene increased in temperature to approximately −153°F., Point B. At this temperature amorphous solidification was observed.Accordingly, −153° F. was determined to be the nominal freezing pointtemperature for the d-limonene.

The solid phase of the d-limonene tested is shown as Zone II in FIG. 2.The solid 20 phase began at approximately −153° F., Point 13. During theabout one minute following Point B, significant solidification occurredresulting in the gelation of the d-limonene. The solidification of thed-limonene was accompanied by an increase in temperature. The gelationor solidification of the d-limonene ended at about one minute after itsfreezing point temperature was reached, or about 24 minutes into theexperiment, Point C. The temperature of the d-limonene was approximately−113° F. when freezing was complete. During the solid phase in Zone IIbetween Points C and D, the d-limonene was warmed to approximately −110°F. by the absorption of heat from the atmosphere surrounding the testapparatus. This solid phase existed for approximately seven to eightminutes. The d-limonene began to melt when its temperature reached about−110° F., Point D. After about four minutes, the melting was complete,Point E.

The second liquid phase of the d-limonene tested is shown as Zone III inFIG. 2. The second liquid phase began at about −110° F., Point E.Accordingly, the melting point temperature of the d-limonene wasdetermined to be approximately −110° F. Thus, as a result of thisexperimental analysis of the commercially available d-limonene, it wasdetermined that d-limonene has a freezing point temperature of about−153° F. and a melting point temperature of about −110° F. Note,however, that the freezing point temperature of commercially availabled-limonene is not consistent, namely it varies depending upon whatimpurities are present and on the degree of agitation provided.Notwithstanding, the melting point temperature of the commerciallyavailable d-limonene was consistently about −110° F.

An identical test using the same test apparatus was performed onterpinolene to determine its freezing point and melting pointtemperatures. The terpinolene was determined to have a freezing pointtemperature of about −134° F. and to have a melting point temperature ofabout −95° F.

Furthermore, the same test apparatus was used to determine the freezingpoint and melting point temperatures of two alkylbenzenes, namely cumeneand diethyl benzene. The cumene tested was obtained from AldrichChemicals. The freezing point temperature and the melting pointtemperature of the cumene tested was determined to be the sametemperature, namely about −145° F. The diethyl benzene tested was alsoobtained from Aldrich Chemicals and was actually a mixture of threeisomers, namely 1,2-diethyl benzene; 1,3-diethyl benzene; and1,4-diethyl benzene. The freezing point and the melting pointtemperatures of the diethyl benzene tested were determined to be theabout −148° F. and about −130° F., respectively.

It has been surprisingly found that alkylbenzenes can be mixed withterpenes to obtain heat transfer fluid compositions that exhibitcharacteristics which are superior to either component alone.Specifically, various mixtures of terpenes can be cooled to temperaturesas low as −175° F. without freezing. The viscosity of these mixtures,however, varies at the reduced temperatures. It has been discovered thatmixtures of terpene and alkylbenzene produce distinctly differentphysical properties as compared to either terpenes or alkylbenzenesalone. Particularly, it has been discovered that certain heat transferfluid compositions comprising a terpene component, comprising at leastone terpene. and an alkylbenzene component, comprising at least onealkylbenzene, exhibit freezing point temperatures that are lower thaneither the terpene or the alkylbenzene component alone.

The heat transfer fluid compositions of the invention comprise (a) aterpene component, comprising at least one terpene; and (b) analkylbenzene component, comprising at least one alkylbenzene. Theterpene component and the alkylbenzene component are provided in aneffective amount such that the resultant compositions are suitable foruse as heat transfer liquids for low temperature applications.Specifically, the terpene component and the alkylbenzene component areprovided in an effective amount such that the resultant compositionretains the liquid phase at temperatures from about 0° F. to about −120°F., preferably from about 0° F. to about −175° F.

The terpene component of the heat transfer fluid compositions of theinvention comprises at least one terpene. The at least one terpene maybe selected from the group of terpenes comprising the terpenes listed inTable 2, as well as the derivatives of the listed terpenes. Preferably,the at least one terpene may be selected from the group of terpenesconsisting of d-limonene, terpinolene, α-terpinene, γ-terpinene,myrcene, 3-carene, sabinene, α-pinene and camphene. Most preferably, theat least one terpene may be selected from the group of terpenesconsisting essentially of d-limonene and terpinolene.

TABLE 2 ACYCLIC TERPENES geraniolene myrcene dihydromyrcene ocimeneallo-ocimene MONOCYCLIC TERPENES ρ-menthane carvomenthene menthenedihydroterpinolene dihydrodipentene α-terpinene γ-terpineneα-phellandrene pseudolimonene limonene d-limonene 1-limonene d,l-limonene isolimonene terpinolene isoterpinolene β-phellandreneβ-terpinene cyclogeraniolane pyronane α-cyclogeranioleneβ-cyclogeraniolene γ-cyclogeraniolene methyl-γ-cyclogeranioleneα-pyronene cyclodihydromyrcene β-pyronene γ-pyronene1-ethyl-5,5-dimethyl-1,3- cyclohexadiene 2-ethyl-6,6-dimethyl-1,3-1(7)-ρ-menthene cyclohexadiene 2,5-ρ-menthadiene 2-ρ-menthene3,8-ρ-menthadiene 2,4-ρ-menthadiene 1(7),4(8)-ρ-menthadiene1,2,3,5-tetramethyl-1,3-cyclohexadiene 1,1-dimethylcyclohexane1,2,4,6-tetramethyl-1,3-cyclohexadiene 1,6,6-trimethylcyclohexeneBICYCLIC TERPENES norsabinane northujeneisopropylbicyclo[3.1.0]hex-2-ene β-thujene thujane sabinene α-thujenenorcarane 3,7-thujadiene 3-norcarene 2-norcarene carane 2,4-norcaradiene3-carene 2-carene nonpinane β-carene apopinane 2-norpinene orthodeneapopinene homopinene norpadiene 2-pinene pinane β-pinene 3-pinenehomoverbanene verbenene norcamphane 4-methylene-2-pinene camphaneapocamphane a-fenchene α-fenchane santane santenane camphenilanenorcamphene isocamphane fenchane camphene β-fenchane 2-norborneneβ-fenchene apobornylene bornylene 2,7,7-trimethyl-2-norbornene santenecamphenilene isofenchene isocamphodiene 1,2,3-trimethyl-2-norbomene2,5,5,-trimethyl-2-norbornene

The derivatives of the terpenes listed in Table 2 consist of bothmonocyclic and bicyclic terpene derivatives. The monocyclic terpenederivatives which may be used in the heat transfer fluid compositions ofthe invention include the derivatives of the acyclic and monocyclicterpenes listed in Table 2. There are two basic categories of thesederivatives. The first category includes monocyclic terpenes which maybe readily formed from acyclic terpenes by ring closure and frombicyclic terpenes by ring fission. A monocyclic terpene contains asix-carbon ring and may be considered a derivative of either cyclohexaneor benzene with a common base carbon ring structure of C₁₀11₁₆. Thevarious derivatives fall into a classification of either Type A or TypeB. The Type A group of monocyclic terpenes may be considered derivativesfrom menthane (isopropylmethylcyclohexane) or from cymene(isoprophylmethylbenzene), all of which may be considered propylcompounds based on the carbon ring structure. The Type B monocyclicterpenes may be considered derivatives of dimethylcyclohexane, for whichthere is no trivial name, and may be considered derivatives of methylcompounds based upon the carbon ring structure.

The second category of derivative adds an atom, functional group oranother molecule to the terpene compound. For example the terpenemolecule may be oxygenated; hydrogenated; halogenated; nitrogenated;modified with silicon based compounds; or reacted to incorporate afunctional group such as an hydroxy, ester, ketone, amine, amide, amino,carboxyl or the like.

The bicyclic terpene derivatives which may be used in the heat transferfluid compositions of the invention include the bicyclic derivatives ofthe terpenes listed in Table 2. The various derivatives which may beclassified as bicyclic terpenes fall into four categories, namelythujane (sabinane), carane, α-pinane and bornane (camphane), eachcategory designating a different class of bicyclic structures. Thesebicyclic terpene structures, also consisting of the basic chemical unitC₁₀H₁₆, resemble the menthane Type A monocyclics and may be consideredto be derivatives of propyl compounds with carbon ring structurescontaining a gem-dimethyl configuration with either an isopropyl groupor a hexane or hectane group based upon the carbon ring structure. Asabove, this describes the first derivative type for the bicyclic terpenecompounds. The second derivative type 15 described in connection withthe monocyclic terpenes also describes the second derivative type forbicyclic terpenes. The detailed structure of these terpene hydrocarbonsare described in “Nomenclature for Terpene Hydrocarbons”, Advances inChemistry Series No. 14 (American Chemical Society), 1955, which isincorporated herein by reference.

The alkylbenzene component of the heat transfer fluid compositions ofthe invention comprises at least one alkylbenzene. An alkylbenzene isdefined as a benzene alkylated with a hydrocarbon. The at least onealkylbenzene may be selected from the group of alkylbenzenes comprisingcumene, diethyl benzene, methyl propyl benzene, propyl benzene and butylbenzene.

The heat transfer fluid compositions of the invention may optionallycontain various additives. For example, the fluid compositions of theinvention may optionally contain at least one of an antioxidant, e.g.butylated hydroxy toluene (BHT) and vitamin F; and a stabilizing agent,e.g. hydroquinone.

The invention will now be illustrated by the following Examples, whichare intended to be purely exemplary and not limiting. In each of thefollowing examples the d-limonene used had an assay like that shown inTable 1, above, and is commercially available from Florida Chemicals asfood grade d-limonene; the diethyl benzene used consisted of a mixtureof isomers, namely 1,2-diethyl benzene; 1,3-diethyl benzene and1,4-diethyl benzene, and is commercially available from AldrichChemicals; the cumene used had a purity of 98%, and is commerciallyavailable from Aldrich Chemicals; the terpinolene used had an assay likethat shown in Table 3, and is commercially available from GlidcoOrganics in Florida.

TABLE 3 Component % by weight in Chemical Compound CommercialTerpinolene terpinolene 99% linolool <1% γ-terpinene <1% octanol <1%

The test apparatus and procedure presented above with regard to theanalysis done to determine the freezing/melting point temperaturecharacteristics of commercially available d-limonene were used todetermine the freezing/melting point temperature characteristics of theheat transfer fluid compositions discussed in the following examples. Inconsidering these examples, however, notice should be given to thelimitations in the test apparatus used. Particularly, due to thelimitations in the test apparatus the lowest temperature that could beobtained in the heat transfer fluid compositions tested was about −175°F. Many of the heat transfer fluid compositions tested have freezingpoint temperatures at least as low as −175° F. Due to the limitations ofthe test apparatus it could not be determined how far below −175° F. thefreezing point temperatures of these liquids are. Notwithstanding, itshould be understood by one skilled in the art that the heat transferfluid compositions of the invention may have, and in many instances dohave, freezing point temperatures below −175° F.

EXAMPLE 1

Using the same testing apparatus and procedure as discussed above withregard to d-limonene, tests were performed to determine thefreezing/melting point temperature characteristics of a heat transferfluid composition comprising about 20% by volume diethyl benzene andabout 80% by volume terpinolene. The freezing point temperature for thediethyl benzene/terpinolene composition was determined to be about −157°F.

EXAMPLE 2

Using the same apparatus and procedure as in Example 1, a heat transferfluid composition comprising about 50% by volume cumene in d-limonenewas tested. The composition was cooled to about −175° F. The compositionwas then allowed to warm. No solidification or crystallization wasobserved during either the cooling or the warming cycles. The results ofthe test analysis of the freezing/melting point temperaturecharacteristics of the heat transfer fluid composition comprising about50% by volume cumene in d-limonene is compared with the freezing/meltingcharacteristics of d-limonene in FIG. 3.

EXAMPLE 3

Using the same apparatus and procedures as in Example 1, a heat transferfluid composition comprising about 75% by volume cumene and about 25% byvolume d-limonene was prepared and tested. The composition was cooled toabout −175° F. The composition was then allowed to warm. Nosolidification or crystallization was observed during either the coolingor the warming cycles.

EXAMPLE 4

The test procedure of Example 2 was repeated several times using heattransfer fluid compositions having different volume percentages ofcumene and d-limonene. The behavior of these various compositions wasstudied to determine the preferred volume percent mixture of cumene tod-limonene with regard to the solidification and viscositycharacteristics of the resultant heat transfer fluid composition. It wasobserved that heat transfer fluid compositions containing less thanabout 10% by volume cumene exhibited freezing during the heating cycle(i.e., the composition was cooled to about −175° F. without freezing butupon heating, crystallization was observed at about −165° F.). Likewise,compositions containing more than about 88% by volume cumene exhibitedfreezing during the heating cycle when the temperature rose to about−153° F. However, heat transfer fluid compositions comprising a mixtureof d-limonene and cumene with a cumene content between about 10% andabout 88% by volume were not observed to exhibit any gelation,crystallization or other solidification upon cooling to about −175° F.or upon the subsequent warming of the composition. Hence, heat transferfluid compositions comprising d-limonene and cumene, wherein the cumenecontent is between about 10% and about 88% by volume, have beendetermined to retain the liquid phase under a range of temperatures frombetween about 0° F. and approximately −175° F. Thus, heat transfer fluidcompositions comprising a mixture of cumene and d-limonene in which thecumene content is from about 10% to about 88% by volume may be used inheat transfer process systems with operating temperatures on the heattransfer liquid side down to at least about −175° F.

Several additional experiments were performed using different blends ofterpenes and alkylbenzenes, to demonstrate that the phenomena identifiedregarding heat transfer fluid compositions comprising mixtures of cumeneand d-limonene are common to mixtures of terpenes and alkylbenzenesgenerally. Specifically, the test procedures used in the perviousexamples were performed on heat transfer fluid compositions based onmixtures of varying amounts of terpinolene as the terpene component anddiethyl benzene as the alkylbenzene component. Test results for threespecific terpinolene/diethyl benzene compositions are provided in thenext three examples.

EXAMPLE 5

A heat transfer fluid composition comprising terpinolene and diethylbenzene with a diethyl benzene content of about 10% by volume wasprepared and tested. The freezing point temperature of this compositionwas observed to be about −141° F.

EXAMPLE 6

A heat transfer fluid composition comprising terpinolene and diethylbenzene with a diethyl benzene content of about 40% by volume wasprepared and tested. The freezing point temperature of this compositionwas observed to be about −170° F.

EXAMPLE 7

A heat transfer fluid composition comprising terpinolene and diethylbenzene with a diethyl benzene content of about 60% by volume wasprepared and tested. The freezing point temperature of this compositioncould not be determined because of the limitations of the testingequipment used as discussed previously. However, the composition wascooled down to about −175° F. without any solid formation during coolingor during the subsequent warming cycle. Accordingly, the freezing pointtemperature of this heat transfer fluid composition was determined to bebelow −175° F.

Several additional tests were performed to obtain the lower thresholdconcentration and upper threshold concentration of diethylbenzene interpinolene. It was observed that heat transfer fluid compositionscomprising terpinolene and diethyl benzene with a diethyl benzenecontent of less than about 50% by volume exhibited a freezing pointtemperature above about −175° F. Furthermore, heat transfer fluidcompositions comprising terpinolene and diethyl benzene with a diethylbenzene content in excess of about 70% by volume likewise exhibited afreezing point temperature above about −175° F. during either thecooling or heating cycle. However, heat transfer fluid compositionscomprising a mixture of terpinolene and diethyl benzene with a diethylbenzene content between about 50% and about 70% by volume were notobserved to exhibit any gelation, crystallization or othersolidification upon cooling to about −175° F. or upon subsequentwarming. Hence, heat transfer fluid compositions comprising terpinoleneand diethyl benzene in which the diethyl benzene content is betweenabout 50% and about 70% by volume have been determined to remain in theliquid phase at temperatures between about 0° F. and approximately −175°F. Thus, heat transfer fluid compositions comprising a mixture ofterpinolene and diethyl benzene in which the diethyl benzene content isfrom about 50% to about 70% by volume may be used in heat transferprocess systems with operating temperatures on the heat transfer liquidside down to at least about −175° F.

EXAMPLE 8

Likewise, the test apparatus and procedures used in the perviousexamples were used on a series of heat transfer fluid compositions basedon mixtures of varying volume percentages of d-limonene as the terpenecomponent and diethyl benzene as the alkylbenzene component. It wasobserved that heat transfer fluid compositions comprising d-limonene anddiethyl benzene with a diethyl benzene content of less than about 20% byvolume exhibited a freezing point temperature above about −175° F.during the warming cycle. Furthermore, heat transfer fluid compositionscomprising d-lirnonene and diethyl benzene with a diethyl benzenecontent in excess of about 65% by volume likewise exhibited a freezingpoint temperature above about −175° F. during either the cooling or thewarming cycle. However, heat transfer fluid compositions comprising amixture of d-limonene and diethyl benzene with a diethyl benzene contentbetween about 20% and about 65% by volume were not observed to exhibitany gelation, crystallization or other solidification upon cooling toabout −175° F. or upon subsequent warming. Hence, heat transfer fluidcompositions comprising d-limonene and diethyl benzene in which thediethyl benzene content is between about 20% and about 65% by volumehave been determined to remain in the liquid phase at temperaturesbetween about 0° F. and approximately −175° F. Thus, heat transfer fluidcompositions comprising a mixture of d-limonene and diethyl benzene inwhich the diethyl benzene content is from about 20% to about 65% byvolume may be used in heat transfer process systems with operatingtemperatures on the heat transfer liquid side down to at least about−175° F.

With reference to FIG. 5, the terpene/silicone heat transfer fluidcompositions will now be described. Based upon earlier researchconcerning eutectic terpene mixtures and terpene/alkylbenzene mixturesit was determined that these mixtures, in liquid form, were usable asheat transfer fluids for low temperature applications. But thesemixtures were limited to certain minimum temperature levels; −165° F.for the eutectic terpene mixtures and −175° F. for theterpene/alkylbenzene mixtures. It should be recalled that neither of themixtures, in their liquid state or phase could be cooled down below−180° F. because of an significant increase in viscosity of thesemixtures at such low temperature. It was observed that the viscosity ofterpene and alkylbenzene increased exponentially with the lowering oftemperature. However, a liquid mixture which could be cooled down to−200° F. with liquid nitrogen without freezing or gelling was stillneeded.

Thus, the development of still another environmentally friendly heattransfer fluid for lower temperatures, using terpene mixtures, wasundertaken. It was experimentally determined that a eutectic mixture ofa low viscosity silicone (poly(dimethylsiloxane)) fluid and a terpenefluid could be cooled down below −175° F., and could even be cooledbelow −200° F. within certain parameters. The silicone fluid wasselected for its flat viscosity profile, i.e. the viscosity does notincrease rapidly as temperature is lowered. Because silicone fluidsdisplayed a low viscosity at low temperatures, e.g. −150° F. to −160°F., this fluid can be cooled down more readily than a terpene or analkylbenzene. However, silicone fluids have the impeding limitation offreezing above −170° F. Thus, it was necessary to experimentallydetermine whether a eutectic mixture of the terpene and siliconecomponents could be combined as a liquid mixture with a resultantfreezing point of the combined components lower than each of theindividual components. At the same time, the combined components mustalso be able exhibit a low viscosity to be cooled down to a temperaturebelow −200°, and to as low a temperature as −222° F.

Following are a number of Examples in which terpene component(s) andsilicone component(s) are combined in liquid mixture and experimentalmeasurements taken. The experimental procedure was the same as thatdescribed above for the terpene/alkylbenzene Examples. Three siliconefluids were selected for trial based upon viscosity and density.

EXAMPLE 9

It was observed that 100% poly(dimethylsiloxane) [silicone] having aviscosity of 1.6 cSt and a density of 0.855 at room temperature formedsolids at −168° F. Both the freezing and melting points are atapproximately −168° F.

EXAMPLE 10

It was observed that 100% poly(dimethylsiloxane) [silicone] having aviscosity of 5.0 cSt and a density of 0.913 at room temperaturesubstantially completely gelled at −167° F.

EXAMPLE 11

It was observed that 100% poly(dimethylsiloxane) [silicone] having aviscosity of 10.0 cSt and a density of 0.93 at room temperature froze at−103° F. and melted around −90° F.

EXAMPLE 12

It was observed that a heat transfer fluid composition comprising 50%d-limonene and 50% silicone (1.6 cSt) by volume achieved a maximum lowtemperature of −222° F. by controlled liquid nitrogen flow through thecooling coil. No freezing or gelling was observed during the cooling orthe warming phase. See FIG. 5.

In FIG. 5 the freezing/melting curves of pure d-limonene (96.5%) and a50% d-limonene and 50% silicone (1.6 cSt) mixture are compared over a1.5 hours. The pure d-limonene freezes at approximately −148° F., asexpected. The 50/50 mixture of d-limonene and silicone continues to becooled down to −222° F. before being allowed to warm. There was noevidence of freezing or gelling detected upon view of the coolingvessel. Other concentrations of mixtures of d-limonene and silicone (1.6cSt) were tried with the following results.

EXAMPLE 13

It was observed that a heat transfer fluid composition comprising 10%d-limonene and 90% silicone (1.6 cSt) by volume remained in a liquidphase and did not freeze when cooled down to −203° F. Although it wouldhave been possible, no attempt was made to continue to cool the liquidbelow the stated temperature. No freezing or gelling was observed duringthe cooling or warming phases.

EXAMPLE 14

A heat transfer fluid composition comprising 90% d-limonene and 10%silicone (1.6 cSt) was cooled to −182° F. It was observed that theliquid became very viscous, however, no freezing or gelling occurredduring the cooling or warming phases.

EXAMPLE 15

A heat transfer fluid composition comprising 50% d-limonene and 50%silicone (5.0 cSt) was cooled to −175° F. It was observed that theliquid was very viscous, but not frozen at that temperature.

EXAMPLE 16

A heat transfer fluid composition comprising 50% d-limonene and 50%silicone (10.0 cSt) was observed to freeze between −150° F. and −161° F.The melting point of this fluid was observed to be approximately −112°F.

It is apparent from the foregoing Examples that a low viscosity siliconefluid, i.e. less than 10.0 cSt, can be added to a terpene fluid to lowerthe freezing point of the mixture. The testing of the variousexperimental heat transfer fluids proved that the lower the viscosity ofthe silicone fluid, the lower the temperature to which the mixture canbe cooled without freezing or gelling. With a lower fluid viscosity, theheat transfer efficiency from the cooling fluid remains constant ratherthan being reduced as viscosity increases.

Another aspect of the invention resides in the industrial application ofthe heat transfer fluid compositions of the invention in heat transferprocess systems. In order to illustrate the industrial utility of thisinvention reference should be made to FIG. 4. FIG. 4 depicts a closedloop cooling system (12) comprised of a pump (14), a jacketed vessel(16) holding the object to be cooled (18), a heat exchanger orevaporator (20), and a coolant expansion container (22). Heat transferliquid (10) comprises a heat transfer fluid composition comprising (a) aterpene component, comprising at least one terpene; and (b) analkylbenzene component, comprising at least one alkylbenzene wherein thesaid components are provided in an effective amount such that theresultant composition remains in the liquid phase at temperatures m therange from about 0° F. to below about −120° F., preferably from about 0°F. to about −175° F. The circulation pump (14) draws the liquid (10)from the expansion or storage container (22) and impels the heattransfer liquid (10) through the jacket of the coolant reactor vessel(16) containing the object to be cooled (18). The heat transfer liquid(10) passes through the reactor jacket causing the reduction 15 intemperature of the object material (18) and passes to the heat exchanger(20). The heat exchanger (20) removes the absorbed heat transferred fromthe object to be cooled (18) in the cooler or chiller reactor (20) bymeans of heat extraction or cooling by subjecting the heat transferliquid (10) to a cryogenic fluid (24) such as liquid nitrogen and liquidcarbon dioxide or an ultra low temperature refrigerant used in amechanical refrigeration system, i.e., R-13, R-14, R-23, R-503 andR-508. The cooled heat transfer liquid (10) then returns to thestorage/expansion container (22) for recirculation and reuse in thecooling system.

A temperature control device is used to modulate the flow of thecryogenic fluid or refrigerant (24) to maintain the temperature of therecirculating heat transfer liquid (10) at a temperature below about 0°F., preferably below about −120° F., most preferably of about −175° F.The recirculated heat transfer liquid (10) is again pumped to thereactor jacket (16) where it absorbs thermal energy from the object tobe cooled (18) in the reactor (16). This causes the heat transfer liquid(10) to increase in temperature. The process is repeated for as long asis necessary until the object to be cooled is cooled to the desiredtemperature.

The utility of the heat transfer fluid compositions of the invention liein making available heat transfer liquids with superior physicalproperties and performance characteristics over currently available heattransfer liquids. Unlike existing heat transfer liquids, the heattransfer fluid compositions of the invention are non-toxic,non-hazardous, and biodegradable. The heat transfer fluid compositionsof the invention provide for lower operating temperatures than can beachieved with presently available commercially viable heat transferliquids. The heat transfer fluid compositions of the invention are ofimmense value to industries which require very low temperatures forprocess control, condensation, freeze drying, environmentalconditioning, and cold storage. The heat transfer fluid compositions ofthe invention provide a solution to these needs with safe, economical,and environmentally friendly chemical components.

The present invention may be embodied in other specific forms withoutdeparting from the spirit or essential attributes thereof. Accordingly,the described embodiments are to be considered in all respects as beingillustrative and not restrictive, with the scope of the invention beingindicated by the appended claims, rather than the foregoing detaileddescription, as indicating the scope of the invention as well as allmodifications which may fall within a range of equivalency which arealso intended to be embraced therein.

1. A heat transfer fluid composition consisting essentially of: (a) 10%to 90% by volume of at least one terpene component; and (b) 90% to 10%by volume of polydimethylsiloxane, in complementary proportionalpercentage amounts to retain the composition in its liquid phase at anytemperature in the entire range from about 0° F. to about −200° F. 2.The heat transfer fluid composition of claim 1, wherein the at least oneterpene is selected from the group consisting of acyclic terpenes,monocyclic terpenes and bicyclic terpenes.
 3. The heat transfer fluidcomposition of claim 2, wherein the acyclic terpenes are composed ofgeraniolene; myrcene; dihydromyrcene; ocimene and allo-ocimene.
 4. Theheat transfer fluid composition of claim 2, wherein the monocyclicterpenes are composed of ρ-menthane; carvomethene; methene,dihydroterpinolene; dihydrodipentene; α-terpinene; γ-terpinene;α-phellandrene; pseudolimonene; limonene; d-limonene; 1-limonene;d,1-limonene; isolimonene; terpinolene; isoterpinolene; β-phellandrene;β-terpinene; cyclogeraniolane; pyronane; α-cyclogeraniolene;β-cyclogeraniolene; γ-cyclogeraniolene; methyl-γ-pyronene;1-ethyl-5,5-dimethyl-1,3-cyclohexadiene;2-ethyl-6,6-dimethyl-1,3-cyclohexadiene; 2-ρ-menthene;1(7)-ρ-methadiene; 3,8-ρ-menthene; 2,4-ρ-menthadiene; 2,5-ρ-menthadiene;1(7),4(8)-ρ-methadiene; 3,8-ρ-menthadiene;1,2,3,5-tetramethyl-1-3-cyclohexadiene;1,2,4,6-tetramethyl-1,3-cyclohexadiene; 1,6,6-trimethylcyclohexene and1,1-dimethylcyclohexane.
 5. The heat transfer fluid composition of claim2, wherein the bicyclic terpenes are composed of norsabinane;northujene; 5-isopropylbicyclohex-2-ene; thujane; β-thujene; α-thujene;sabinene; 3,7-thujadiene; norcarane; 2-norcarene; 3-norcarene;2-4-norcaradiene; carane; 2-carene; 3-carene; β-carene; nonpinane;2-norpinene; apopinane; apopinene; orthodene; norpadiene; homopinene;pinane; 2-pinene; 3-pinene; β-pinene; verbenene; homoverbanene;4-methylene-2-pinene; norcamphane; apocamphane; campane; α-fenchane;α-fenchene; santenane; santane; norcamphene; camphenilane; fenchane;isocamphane; β-fenchane; camphene; β-fenchane; 2-norbornene;apobornylene; bornylene; 2,7,7-trimethyl-2-norbornene; santene;1,2,3,-trimethyl-2-norbornene; isocamphodiene; camphenilene; isofencheneand 2,5,5-trimethyl-2-norbornene.
 6. The heat transfer fluid compositionof claim 1, wherein the at least one terpene is selected from the groupconsisting of d-limonene, terpinolene, α-terpinene, γ-terpinene,myrcene, 3-carene, sabinene, α-pinene and camphene.
 7. The heat transferfluid composition of claim 1, wherein the polydimethylsiloxane has aviscosity less than 10.0 cSt.
 8. The heat transfer fluid composition ofclaim 1, wherein the terpene component consists essentially ofd-limonene and the polydimethylsiloxane has a viscosity of 1.6 cSt. 9.The heat transfer fluid composition of claim 1, wherein the compositionfurther consists of at least one antioxidant and a stabilizing agent.10. A low temperature heat transfer process using a heat transfer fluidcomposition comprising the steps of: a. transferring thermal energy fromthe heat transfer fluid composition to a cooling fluid such that theheat transfer fluid composition is cooled to a temperature between about0° and about −200° F.; b. transferring thermal energy from an object tobe cooled to the heat transfer fluid composition; and, c. repeating (a)and (b) until said object is cooled to the desired temperature; whereinsaid heat transfer fluid composition consisting essentially of: (a) 10%to 90% by volume of at least one terpene component; and (b) 90% to 10%by volume of polvdimethylsiloxane; in complementary proportionalpercentage amounts to retain the composition in its liquid phase at anytemperature in the entire range from about 0° F. to about −200° F. 11.The process of claim 10, wherein the thermal energy is transferred fromthe heat transfer fluid composition to at least one cryogenic fluid or arefrigerant.
 12. The process of claim 10, wherein the process isoperated under conditions such that the temperature of the heat transfercomposition ranges from about 0° F. to between about −150° F. and about−200° F.
 13. The process of claim 10, wherein the at least one terpeneis selected from the group consisting of acyclic terpenes, monocyclicterpenes and bicyclic terpenes.
 14. The process of claim 13, wherein theacyclic terpenes are composed of geraniolene; myrcene; dihydromyrcene;ocimene and allo-ocimene.
 15. The process of claim 13, wherein themonocyclic terpenes are composed of ρ-menthane; carvomethene; methene,dihydroterpinolene; dihydrodipentene; α-terpinene; γ-terpinene;α-phellandrene; pseudolimonene; limonene; d-limonene; 1-limonene,d,1-limonene; isolimonene; terpinolene; isoterpinolene; β-phellandrene;β-terpinene; cyclogeraniolane; pyronane; α-cyclogeraniolene;β-cyclogeraniolene; γ-cyclogeraniolene; methyl-γ-pyronene;1-ethyl-5,5-dimethyl-1,3-cyclohexadiene;2-ethyl-6,6-dimethyl-1,3-cyclohexadiene; 2-ρ-menthene;1(7)-ρ-methadiene; 3,8-ρ-menthene; 2,4-ρ-menthadiene; 2,5-ρ-menthadiene;1(7),4(8)-ρ-methadiene; 3,8-ρ-menthadiene;1,2,3,5-tetramethyl-1-3-cyclohexadiene;1,2,4,6-tetramethyl-1,3-cyclohexadiene; 1,6,6-trimethylcyclohexene and1,1-dimethylcyclohexane.
 16. The process of claim 13, wherein thebicyclic terpenes are composed of norsabinane; northujene;5-isopropylbicyclohex-2-ene; thujane; β-thujene; α-thujene; sabinene;3,7-thujadiene; norcarane; 2-norcarene; 3-norcarene; 2-4-norcaradiene;carane; 2-carene; 3-carene; β-carene; nonpinane; 2-norpinene; apopinane;apopinene; orthodene; norpadiene; homopinene; pinane; 2-pinene;3-pinene; β-pinene; verbenene; homoverbanene; 4-methylene-2-pinene;norcamphane; apocamphane; campane; α-fenchane; α-fenchene; santenane;santane; norcamphene; camphenilane; fenchane; isocamphane; β-fenchane;camphene; β-fenchane; 2-norbornene; apobornylene; bornylene;2,7,7-trimethyl-2-norbornene; santene; 1,2,3,-trimethyl-2-norbornene;isocamphodiene; camphenilene; isofenchene and2,5,5-trimethyl-2-norbornene.
 17. The process of claim 10, wherein theat least one is selected from the group consisting of d-limonene,terpinolene, α-terpinene; γ-terpinene, myrcene, 3-carene, sabinene,α-pinene and camphene and the polydimethylsiloxane has a viscosity lessthan 10.0 cSt.